Yang Qianqian, Li Xiao-Lei, Ashebr Tesfay G, Zhao Lang, Tang Jinkui
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, P. R. China.
School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, 230026, P. R. China.
Chem Asian J. 2022 Aug 15;17(16):e202200496. doi: 10.1002/asia.202200496. Epub 2022 Jul 11.
The construction of metallosupramolecules is an interesting but challenging topic for chemists. Dedicated design of multidentate ligands is an effective approach for the construction of novel lanthanide supramolecules. Herein, we report on the stepwise design and syntheses of two flexible and multidentate ligands H L and H L based on the o-vanillin. By regulating the coordination sites and mode of the ligands, two novel Dy -based supramolecules, [Dy Na(μ -OH) L (H O) (CH OH)](CF SO ) ⋅ 3H O ⋅ CH OH (Dy ) and [Dy L (H L ) (H O) ] ⋅ 4CH OH ⋅ 12H O (Dy ), have been obtained. Structural studies reveal that Dy and Dy show different nuclearity and topology: Dy shows a crescent-like structure coordinated by the ligands in different coordination fashions in which two ligands chelate Dy forming {Dy } units and linked by the other two ligands; Dy is obtained from the supramolecular assembly, in which four completely deprotonated ligands construct the {Dy } units and the units are linked by four di-deprotonated ligands, forming a macrocycle topology. Additionally, magnetic measurements reveal that the two complexes exhibit slow magnetic relaxation behavior.
金属超分子的构建对化学家来说是一个有趣但具有挑战性的课题。多齿配体的专门设计是构建新型镧系超分子的有效方法。在此，我们报道了基于邻香草醛的两种柔性多齿配体HL和HL的逐步设计与合成。通过调节配体的配位位点和模式，得到了两种新型的基于Dy的超分子，DyNa(μ-OH)L(H₂O)(CH₃OH)₂⋅3H₂O⋅CH₃OH (Dy₁) 和 [DyL₂(H₂L)(H₂O)₂]⋅4CH₃OH⋅12H₂O (Dy₂)。结构研究表明，Dy₁和Dy₂呈现出不同的核数和拓扑结构：Dy₁呈现出一种月牙状结构，配体以不同的配位方式与之配位，其中两个配体螯合Dy形成{Dy₂}单元，并通过另外两个配体相连；Dy₂是通过超分子组装得到的，其中四个完全去质子化的配体构建{Dy₄}单元，这些单元通过四个双去质子化的配体相连，形成大环拓扑结构。此外，磁性测量表明这两种配合物表现出慢磁弛豫行为。
